AU2007253912B2

AU2007253912B2 - Aqueous non-ionic hydrophilic polyurethane dispersions, and a continuous process of making the same

Info

Publication number: AU2007253912B2
Application number: AU2007253912A
Authority: AU
Inventors: Mark Adams; Debkumar Bhattacharjee; Bedri Erdem; Robert C. Frye; Duane R. Roberts
Original assignee: Dow Global Technologies LLC
Current assignee: Dow Global Technologies LLC
Priority date: 2006-05-16
Filing date: 2007-05-08
Publication date: 2013-12-19
Anticipated expiration: 2027-05-08
Also published as: JP2009537667A; WO2007136991A1; AU2007253912A1; CA2651511A1; EP2021393A1; KR20090026765A; US20090105411A1; BRPI0710995A2; CN101443379A; MX2008014617A; RU2008149515A

Abstract

The instant invention is an aqueous non-ionic hydrophilic polyurethane dispersion, and a continuous process for making the same. The aqueous non-ionic hydrophilic polyurethane dispersion according to instant invention includes the reaction product of a non- ionic hydrophilic prepolymer, water, optionally an external surfactant, and optionally a chain-extending reagent. The non-ionic hydrophilic prepolymer includes the reaction product of a first component and a second component. The first component is selected from the group consisting of an aromatic polyisocyanate, an aliphatic polyisocyanate, and combinations thereof. The second component is a hydrophilic alkylene oxide polyol, a non-ionic hydrophilic alkylene oxide monol, or combinations thereof. The continuous process for producing the non-ionic hydrophilic aqueous polyurethane dispersion includes the following steps: (1) providing a disperse phase liquid stream having a flow rate R

Description

WO 2007/136991 PCT/US2007/068466 AQUEOUS NON-IONIC HYDROPHILIC POLYURETHANE DISPERSIONS, AND A CONTINUOUS PROCESS OF MAKING THE SAME Field of Invention 5 The instant invention relates to an aqueous non-ionic hydrophilic polyurethane dispersion, and a continuous process for making the same. Cross-Reference to Related Applications This application is a non-provisional application claiming priority from the U.S. Provisional Patent Application Ser. No. 60/800,793, filed on May 16, 2006 entitled 10 "AQUEOUS NON-IONIC HYDROPHILIC POLYURETHANE DISPERSIONS, AND A CONTINUOUS PROCESS OF MAKING THE SAME," the teachings of which are incorporated herein as if reproduced in full hereinbelow. Background of the Invention Aqueous polyurethane dispersions are generally well known and are used in the 15 production of useful polyurethane products. Different techniques have been employed to facilitate the production of aqueous polyurethane dispersions. U.S. Patent No. 6,897,281 describes a breathable polyurethane having an upright moisture vapor transmission rate of more than about 500 gms/m 2 /24 hr. The breathable polyurethane includes: (a) poly(alkylene oxide) side-chain units in an amount comprising 12 20 weight percent to 80 weight percent of the polyurethane, wherein (i) alkylene oxide groups in the poly(alkylene oxide) side-chain units have from 2 to 10 carbon atoms and are unsubstituted, substituted, or both unsubstituted and substituted, (ii) at least about 50 weight percent of the alkylene oxide groups are ethylene oxide, and (iii) the amount of the side-chain units is at least about 30 weight percent when the molecular weight of the side-chain units is 25 less than about 600 grams/mole, at least about 15 weight percent when the molecular weight of the side-chain units is from 600 to 1,000 grams/mole, and at least about 12 weight percent when the molecular weight of the side-chain units is more than about 1,000 grams/mole, and (b) poly(ethylene oxide) main-chain units in an amount including less than about 25 weight percent of the polyurethane. 30 U.S. Patent No. 5,700,867 describes an aqueous dispersion of an aqueous polyurethane having an ionic functional group, polyoxyethylene units, and terminal hydrazine functional groups. Content of the ionic functional group is 5 to 180 milliequivalent per 100 g

I

of the aqueous polyurethane, and content of the polyoxyethylene unit is about 20 percent by weight or less of a weight of the aqueous polyurethane. U.S. Patent No. 5,043,381 describes an aqueous dispersion of a non-ionic water dispersible polyurethane having pendent polyoxyethylene chains, and one crosslink per 3,000 5 to 100,000 atomic weight units. U.S. Patent No. 4,092,286 describes water-dispersible polyurethane elastomers having a substantially linear molecular structure characterized by (a) lateral polyalkylene oxide polyether chains having a content of ethylene oxide units of from about 0.5 to 10 percent by weight, based on the polyurethane as a whole and (b) a content of ionic groups of from about 10 0.1 to 15 milliequivalents per 100 g. U.S. Patent No. 3,920,598 describes a polyurethane, which is adapted to be dispersed in water without an emulsifier. The polyurethane, adapted to be dispersed in water without an emulsifier, is prepared by reacting an organic compound having reactive hydrogen atoms determinable by the Zerewitinoff method with an organic diisocyanate having a side chain 15 which contains repeating (-O-CH 2

-CH

2 ) groups. Japanese Patent Disclosure No. 57-39212 describes a method of molding polyurethanes in which an aqueous emulsion of polyurethane with a specific structure is solidified via heat treatment. The aqueous emulsion of polyurethane is the product of a prepolymer obtained by reacting (a) polyisocyanate; (b) polyoxyethylene glycol compounds 20 with molecular weights of 800-1500, at 6-30 weight percent; and (c) polyhydroxyl compounds other than (ii). Despite the research efforts in developing and improving aqueous polyurethane dispersions, there is still a need for further improved aqueous polyurethane dispersions, and method of making thereof. 25 Where the terms "comprise", "comprises", "comprised" or "comprising" are used in this specification (including the claims) they are to be interpreted as specifying the presence of the stated features, integers, steps or components, but not precluding the presence of one or more other features, integers, steps or components, or group thereof. The discussion of documents, acts, materials, devices, articles and the like is included 30 in this specification solely for the purpose of providing a context for the present invention. It 2 is not suggested or represented that any or all of these matters formed part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed before the priority date of each claim of this application. 5 Summary of the Invention The instant invention is an aqueous non-ionic hydrophilic polyurethane dispersion, and a continuous process for making the same. The aqueous non-ionic hydrophilic polyurethane dispersion according to instant invention includes the reaction product of a non-ionic hydrophilic prepolymer, water, optionally an external surfactant, and optionally a chain 10 extending reagent. The non-ionic hydrophilic prepolymer includes the reaction product of a first component and a second component. The first component is selected from the group consisting of an aromatic polyisocyanate, an aliphatic polyisocyanate, and combinations thereof. The second component is a hydrophilic alkylene oxide polyol, a non-ionic hydrophilic alkylene oxide monol, or combinations thereof. The continuous process for 15 producing the non-ionic hydrophilic aqueous polyurethane dispersion includes the following steps: (1) providing a disperse phase liquid stream having a flow rate R 2 , wherein the disperse phase liquid stream contains a non-ionic hydrophilic polyurethane prepolymer comprising the reaction product of (a) a first component, wherein the first component is an aromatic polyisocyanate, aliphatic polyisocyanate, or combinations thereof; and (b) a second 20 component, wherein the second component is a non-ionic hydrophilic alkylene oxide polyol, a non-ionic hydrophilic alkylene oxide monol, or combinations thereof, (2) providing a continuous phase liquid stream having a flow rate R 1 , wherein the continuous phase liquid stream comprising water and optionally a surfactant; (3) continuously merging the disperse phase liquid stream and the continuous phase liquid stream into a high-shear disperser, 25 wherein R 2 :R is in the range of 10:90 to 30:70; (4) emulsifying the non-ionic hydrophilic polyurethane prepolymer in the water via a high-shear disperser; and (5) thereby producing the non-ionic hydrophilic aqueous polyurethane dispersion. The instant invention also includes an aqueous non-ionic hydrophilic polyurethane dispersion consisting essentially of the reaction product of: 30 a non-ionic hydrophilic prepolymer consisting essentially of the reaction product of: 3 a first component, wherein said first component is selected from the group consisting of an aromatic polyisocyanate, an aliphatic polyisocyanate, and combinations thereof; and a second component, wherein said second component consists of non 5 ionic hydrophilic ethylene oxide monol or diol; wherein said polyurethane prepolymer includes from 80 to 90 percent by weight of the second component, based on the weight of said polyurethane prepolymer; water; an external surfactant selected from the group consisting of metal and 10 ammonium salts of sulfonates, phosphates and carboxylates; and a chain extending reagent; wherein the aqueous non-ionic hydrophilic polyurethane dispersion has an average particle size ranging from 20 to 1000 nanometers and a polydispersity index ranging from 1.0 to 5.0. 15 The instant invention also provides a continuous process for producing a non-ionic hydrophilic aqueous polyurethane dispersion including the steps of: providing disperse phase liquid stream having a flow rate R 2 , wherein said disperse phase liquid stream containing a non-ionic hydrophilic polyurethane prepolymer includes the reaction product of: 20 a first component, wherein said first component being an aromatic polyisocyanate, aliphatic polyisocyanate, or combinations thereof; and a second component, wherein said second component being a non-ionic hydrophilic alkylene oxide polyol, a non-ionic hydrophilic alkylene oxide monol, or combinations thereof; 25 wherein said polyurethane prepolymer including at least 80 percent by weight of the second component, based on the weight of said polyurethane prepolymer; providing a continuous phase liquid stream having a flow rate R 1 , wherein said continuous phase liquid stream including water; continuously merging said disperse phase liquid stream and said continuous 30 phase liquid stream into a high-shear disperser, wherein R 2 :Rj being in the range of 10:90 to 30:70; 3a emlsifying said noni-ionic hyrpii oyrtaeprepolyrner in said water -via 'a high- slitat aipr~ and. thereby prodtici.ng sAid non-;ionio hydrophilic aquvou~s polyur-ethmnc dispersion. 5 In yet a further asp eel.., tlho instan..t invention provides a coniiwts process for PrOdU.~m no-nk ~~d~~~w uospolyurethiane dispersion, wher-ciri the aqu ous non ionic hydrophilic polyure-Thmne dis-petsion -has aparticle sizc from 20 to 1 000 nim and a polydispcrsity in the% range of* 1 0 to, 5.0, comprisig the step ; of', 0 providing a dtiperse phase liquid stream having ,a flOw ra R. , stid disp~ersed phase liquid kaircarn contafiing a aot- ioic hydropiflic polywcirian prep~oJY1tnef onsisting. of, the reaction product cvfY, a first. component., said fi rsf com-poncnt b6i rig tyri aromatic pplyk oe yanatle, lpaicoyw yfat or cotnhbinlliO2s, thereoff, 5 said armrnW, polyisocyaia-te being selected fiotn the group consistuig of'MI, TDI, and. PMDl, and s.aid & ipJ~ifltic polyisccyarnate- bain. se iwted 1rom-the group consisting of TT, TPDJ1and I11MNDi; tho non-ionic; hydrophific polyurfethanc prcpulymiier comprising utp to 90 perEen '0 by wveighlt ofiAlic first ccrn nie-, based. on the weight of thp nor -ipnio hydro hilib polyurethane pirepol(ymer, and s second omponfeit, said sceond com-ponent beiiia no-n-"Ionic hydrop.hilic alkyke oxide ro)yoJ, a. nowI.-ionic hydro plilic al kyleiac oxide. no1, or CoMbinations thercof; 2'said. hyrpii .~yeeoxide poiyoi rac yhphlcakln oxide. ronol'bcing a lionopolymr.r or a copolymer; ,he,. no0n-i yrde hyfirophil ic plueheprjlvn comprising up to 90 pe rmen. by weight of the second comlponlent, based on tlhc weig1fit of thie tpon-.onic hydro hilic poiyurethanq. prepolymner.; providiing- con)titwous phase- liquid stmriri having a flow rate. R!, said conti 111uou phas.l INquid stream oompuising water and' optionally an externail sur!"actatl; continuously merging said disperse phase liquid stream and said continuous phase liquid stream into a high-shear disperser, wherein R 2 :Rj being in the range of 10:90 to 30:70; emulsifying said non-ionic hydrophilic polyurethane prepolymer in said water 5 via a high-shear disperser; and thereby producing said non-ionic hydrophilic aqueous polyurethane dispersion. Detailed Description of the Invention The aqueous non-ionic hydrophilic polyurethane dispersion according t instant 10 invention includes the reaction product of a non-ionic hydrophilic prepolymer, vater, optionally an external surfactant, and optionally a chain-extending reagent. Th non-ionic hydrophilic prepolymer includes the reaction product of a first component and 4 second component. The first component is selected from the group consisting of an aromatic polyisocyanate, an aliphatic polyisocyanate, and combinations thereof. The second 15 component is a hydrophilic alkylene oxide polyol, a non-ionic hydrophilic alkylene oxide monol, or combinations thereof. The first component may be any known aromatic polyisocyanate, aliphatic polyisocyanate, or combinations thereof. These polyisocyanates include those containing at least about two isocyanate groups per molecule, preferably, those containing an average of ?0 from 2.0 to 3.0 isocyanate groups per molecule. The polyisocyanates may preferably be aromatic polyisocyanate, aliphatic polyisocyanate, or combinations thereof. Exmplary polyisocyanates include, but are not limited to, toluene diisocyanates (TDI), diphenylmethane 4,4'-diisocyanate (MDI), xylylene diisocyanate, naphthalene- 1,5 3c WO 2007/136991 PCT/US2007/068466 diisocyanate, p-phenylene diisocyanate, dibenzyl diisocyanate, diphenyl ether diisocyanate, m- or p-tetramethylxylylene diisocyanate, triphenylmethane triisocyanate. Furthern-ore, aliphatic diisocyanates (which further encompasses alicyclic diisocyanates) include those disclosed in U.S. Patent No. 5,494,960, herein, such as hydrogenated tolylene diisocyanate, 5 hydrogenated diphenylmethane-4,4'-diisocyanate(HI 2 MDI), 1,4-tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), hydrogenated xylylene diisocyanate, cyclohexyl-1, 4 diisocyanate, and isophorone diisocyanate (IPDI) as well as 1,3-and 1,4-bis-(isocyanato methylcyclohexane), and mixtures thereof. In addition, the polyisocyanate may include one or more kinds of any of the referenced isocyanate monomer units. The first component may 10 preferably be selected from the group consisting of MDI, TDI, HDI, and 1,3-and 1,4-bis (isocyanatomethyl) cyclohexane. The second component may be any alkylene oxide polyol, alkylene oxide monol, or combinations thereof; for example, the second component may preferably be a non-ionic hydrophilic alkylene oxide polyol, a non-ionic hydrophilic alkylene oxide monol, and 15 combinations thereof. The alkylene oxide of the alkylene oxide polyol or the alkylene oxide monol may typically be ethylene, or propylene. The alkylene oxide of the alkylene oxide polyol or the alkylene oxide monol may preferably be ethylene. The alkylene oxide polyol or the alkylene oxide monol may be a homopolymer, or a copolymer. The alkylene oxide polyol or the alkylene oxide monol may further be a linear polymer, or a branched polymer. 20 The alkylene oxide moieties of the non-ionic hydrophilic alkylene oxide polyol or non-ionic hydrophilic alkylene oxide monol may either be randomly distributed or block distributed. Such non-ionic hydrophilic alkylene oxide polyols include, but are not limited to, polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, blends thereof, and combinations thereof The second component may preferably be a non 25 ionic hydrophilic polyethylene oxide. The second component may further include non-ionic hydrophobic polyols including, but not limited to, polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, aromatic or aliphatic polyester polyols, polycaprolactone polyols, acrylic polyols, blends thereof, and combinations thereof. The second component may comprise up to 90 percent by weight of the non-ionic hydrophilic 30 alkylene oxide polyol or non-ionic hydrophilic alkylene oxide monol, based on the weight of the second component. All individual values and subranges from 0 to 90 percent by weight are included herein and disclosed herein; for example, the second component may comprise about 10 to 90 percent by weight of the non-ionic hydrophilic alkylene oxide polyol or the non-ionic hydrophilic alkylene oxide monol, based on the weight of the second component; 4 WO 2007/136991 PCT/US2007/068466 or in the alternative, the second component may comprise at least 80 percent by weight of the non-ionic hydrophobic alkylene oxide polyol or the non-ionic hydrophobic alkylene oxide monol, based on the weight of the second component. The non-ionic hydrophilic polyurethane prepolymer may comprise any amounts of 5 either the first component or the second component. The non-ionic hydrophilic polyurethane prepolymer may comprise up to about 90 percent by weight of the first component, based on the weight of the non-ionic hydrophobic polyurethane prepolymer. All individual values and subranges from 0 to 90 percent by weight are included herein and disclosed herein; for example, the non-ionic hydrophilic polyurethane prepolymer may comprise up to about 50 10 percent by weight of the first component, based on the weight of the non-ionic hydrophilic polyurethane prepolymer; or in the alternative, the non-ionic hydrophilic polyurethane prepolymer may comprise up to about 20 percent by weight of the first component, based on the weight of the non-ionic hydrophilic polyurethane prepolymer. Furthermore, the non-ionic hydrophilic polyurethane prepolymer may comprise up to about 90 percent by weight of the 15 second component, based on the weight of the non-ionic hydrophilic polyurethane prepolymer. All individual values and subranges from 0 to 90 percent by weight are included herein and disclosed herein; for example, the second component may comprise about 10 to 90 percent by weight of the non-ionic hydrophilic alkylene oxide polyol or the non-ionic hydrophilic alkylene oxide monol, based on the weight of the second component; or in the 20 alternative, the second component may comprise at least 80 percent by weight of the non ionic hydrophobic alkylene oxide polyol or the non-ionic hydrophobic alkylene oxide monol, based on the weight of the second component. The non-ionic hydrophilic polyurethane prepolymer may comprise up to about 10 percent by the combined weight of the additional components, based on the weight of the non-ionic hydrophilic polyurethane prepolymer. All 25 individual values and subranges from 0 to 10 percent by weight are included herein and disclosed herein; for example, the non-ionic hydrophilic polyurethane prepolymer may comprise up to about 5 percent by the combined weight of the additional components, based on the weight of the non-ionic hydrophilic polyurethane prepolymer. The aqueous non-ionic hydrophilic polyurethane dispersion may comprise any 30 amount of the non-ionic hydrophilic polyurethane prepolymer; for example, the aqueous non ionic hydrophilic polyurethane dispersion may comprise up to about 70 percent by weight of the non-ionic hydrophilic polyurethane prepolymer, based on weight of the aqueous non ionic hydrophilic polyurethane dispersion. All individual values and subranges from 0 to 70 percent by weight are included herein and disclosed herein; for example, the aqueous non 5 WO 2007/136991 PCT/US2007/068466 ionic hydrophilic polyurethane dispersion may comprise up to about 30 percent by weight of the non-ionic hydrophilic polyurethane prepolymer, based on weight of the aqueous non ionic hydrophilic polyurethane dispersion; or in the alternative, the aqueous non-ionic hydrophilic polyurethane dispersion may comprise up to about 20 percent by weight of the 5 non-ionic hydrophilic polyurethane prepolymer, based on weight of the aqueous non-ionic hydrophilic polyurethane dispersion. For example, the aqueous non-ionic hydrophilic polyurethane dispersion may comprise up to about 10 percent by weight of the non-ionic hydrophilic polyurethane prepolymer, based on weight of the aqueous non-ionic hydrophilic polyurethane dispersion. Furthermore, the non-ionic hydrophilic polyurethane dispersion 10 may comprise any amount of water; for example, the non-ionic hydrophilic polyurethane dispersion may comprise 30 to 90 percent by weight of water, based on weight of the aqueous non-ionic hydrophilic polyurethane dispersion. All individual values and subranges from 30 to 90 percent by weight are included herein and disclosed herein; for example, the non-ionic hydrophilic polyurethane dispersion may comprise 70 to 90 percent by weight of water, based 15 on weight of the aqueous non-ionic hydrophilic polyurethane dispersion; or in the alternative, the aqueous non-ionic hydrophilic polyurethane dispersion may comprise 80 to 90 percent by weight of water, based on weight of the aqueous non-ionic hydrophilic polyurethane dispersion . The aqueous non-ionic hydrophilic polyurethane dispersion may optionally include 20 one or more surfactants. Such surfactants are typically included in the water phase. The surfactant may, for example, be anionic, non-ionic, cationic, zwitterionic, or a mixture of non-ionic with cationic, anionic or zwitterionic. Preferred surfactants are non-ionic, and anionic surfactants. The surfactant, which is not incorporated into the polymer backbone, is selected from the group consisting of metal or arnmonium salts of sulfonates, phosphates and 25 carboxylates. Suitable surfactants include alkali metal salts of fatty acids such as sodium stearate, sodium palmitate, potassium oleate, alkali metal salts of fatty acid sulfates such as sodium lauryl sulfate, the alkali metal salts of alkylbenzenesulfate and alkylbenzenesulfonate, and alkylnaphthalenesulfate and alkylnaphthalenesulfate, such as sodium dodecylbenzenesulfonate, sodium alkylnaphthalene-sulfonate; the alkali metal salts of 30 dialkyl-sulfosuccinates; the alkali metal salts of sulfated alkylphenol ethoxylates such as sodium octylphenoxypolyethoxyethyl sulfate; the alkali metal salts of polyethoxyalcohol sulfates and the alkali metal salts of polyethoxyalkylphenol sulfates. More preferably, the anionic surfactant may be sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, sodium dodecyl diphenyl oxide disulfonate, sodium n-decyl diphenyl oxide disulfonate, 6 WO 2007/136991 PCT/US2007/068466 isopropylamine dodecylbenzenesulfonate, or sodium hexyl diphenyl oxide disulfonate, and most preferably, the anionic surfactant may be sodium dodecyl benzene sulfonate. Non-ionic surfactants may, for example, be ethylene oxide adducts of phenols, such as nonyl phenol, and ethoxylated fatty acids, ethoxylated fatty acids ester, glycol ester, and combinations 5 thereof. The aqueous non-ionic hydrophilic polyurethane dispersion may optionally comprise from 0 to about 6 percent by weight of a surfactant, based on the total weight of the aqueous non-ionic hydrophilic polyurethane dispersion. All individual values and subranges from 0 to 6 percent by weight are included herein and disclosed herein; for example, the aqueous non-ionic hydrophilic polyurethane dispersion may optionally comprise from 0.05 to 10 about 5 percent by weight of a surfactant, based on the total weight of the aqueous non-ionic hydrophilic polyurethane dispersion. In general, it is desired to add a sufficient amount of surfactant to facilitate the production of an aqueous non-ionic hydrophilic dispersion having an average particle size in the range of 20 to 1000 nm, more preferably 40 to 150 nm, and a polydispersity in the range of 1.0 to 5.0, and more preferably 1.0 to 2.0. Surfactants, 15 preferably externally added, play an important role in the formation and stabilization of emulsions, and dispersions. Generally, higher surfactant concentrations result in smaller diameter particles, but surfactant concentrations that are too high tend to deleteriously affect the properties of products. A person of ordinary skill in the art can readily determine the appropriate surfactant type and concentration for the particular process and end use. 20 Although water can be used as a chain-extending agent, the polyurethane dispersion of the instant invention may further include other chain-extending agents without incorporating any ionic properties into the polyurethane particles such as aliphatic, cycloaliphatic, aromatic polyamines, and alcohol amines for building of molecular weight. Therefore, the prepolymer may preferably be contacted with a chain-extending agent before 25 substantial reaction takes place between water and the prepolymer. The chain-extending agents include, but are not limited to, hydrazine, ethylene diamine, hexamethylene diamine, aminated polyoxyalkyleneddiol, 1,3-1,4 bis (aminomethyl) cyclehexane, and isophoronediamine. The aqueous non-ionic hydrophilic polyurethane dispersion according to instant 30 invention may further include other optional additives, such as phase modifiers. Such phase modifiers may be included in the water during the preparation of the non-ionic hydrophilic polyurethane dispersion. Colloidal stability of the non-ionic hydrophilic polyurethane dispersion may be enhanced by including with the water from 0.5 to 8 weight percent of a protective colloid, such as poly(vinyl alcohol), or an anionic surfactant. Such phase 7 WO 2007/136991 PCT/US2007/068466 modifiers are present typically in the amount of from 0.1 to 5 weight percent of the non-ionic hydrophilic polyurethane dispersion. The non-ionic hydrophilic polyurethane dispersion according to instant invention may further include rheology modifiers such as ammonium alginate and methyl cellulose which give desirable flow characteristics; fillers such as clays, 5 carbon black and colloidal silica and talc to modify tensile, abrasion and tear properties; dyes and pigments; antidegradants; and softeners such as mineral oil to control modulus. Additionally, the non-ionic hydrophilic polyurethane dispersion may be blended with other emulsions, and dispersions including, but not limited to, polyolefin dispersions, epoxy dispersions, acrylic dispersions, styrene/butadiene dispersions, combinations thereof. 10 The non-ionic hydrophilic polyurethane dispersion according to instant invention may further include any other additive which is known to those of ordinary skill in the end-use to which the inventive polyurethane dispersions are applied can be used so long as their presence does not degrade the desired properties of the end-use product. Such additives can be incorporated into the dispersions in any way known to be useful including, but not limited 15 to, inclusion in the prepolymer formulation and inclusion in the water used to make the dispersion. Other suitable additives include titanium dioxide, calcium carbonate, silicon oxide, defoamers, biocides, carbon particles. In production, the aqueous non-ionic hydrophilic polyurethane dispersion of the instant invention is made by mixing the prepolymer with water, optionally in the presence of 20 a surfactant, optionally other additives and/or phase modifiers, and/or optionally a chain extending agent, at a temperature of from 10 to 90 'C, to render the desired aqueous non ionic hydrophilic polyurethane dispersion. An excess amount of water may be used to control the solid content. The aqueous non-ionic hydrophilic polyurethane prepolymer may be prepared by a 25 batch, or a continuous process. For example, in a continuous process, a stoichiometric excess of an aromatic or aliphatic polyisocyanate, and non-ionic hydrophilic ethylene oxide polyol or monol may be introduced in separate streams into a static or an active mixer, preferably in the absence of a catalyst, and at a temperature suitable for controlled reaction of the reagents, typically from 40 "C to 100 "C at atmospheric pressure. The reaction may be carried to 30 substantial completion in a plug flow reactor to form the non-ionic hydrophilic polyurethane prepolymer. In alternative, for example, in a batch process, non-ionic hydrophilic ethylene oxide polyol or monol is introduced into a reactor. The temperature of the reactor is raised, for example to 70 'C, while agitating the non-ionic hydrophilic ethylene oxide polyol or monol. Aromatic or aliphatic polyisocyanates are added to the reactor in the absence of any 8 WO 2007/136991 PCT/US2007/068466 catalyst, and the temperature of the reactor is being raised, for example to 80 'C while agitation process continues for a certain period of time, for example four hours. In case a catalyst is present, the reaction conditions such as temperature or time required for the reaction to take place may be lowered. 5 The aqueous non-ionic hydrophilic polyurethane dispersions of the instant invention, preferably made as a high internal phase ratio (HIPR) emulsion, contain the reaction product of the non-ionic hydrophilic polyurethane prepolymer (as the dispersed phase) and water (as the continuous phase). When present, the chain-extending agent and/or surfactant appear in the continuous phase. The use of HIPR process renders certain advantages to non-ionic 10 hydrophilic polyurethane dispersions (PUDs), most particularly the ability to produce solvent-free non-ionic hydrophilic polyurethane dispersions from highly reactive (for example aromatic isocyasnates) in the absence of any solvent. Furthermore, HIPR process does not require to use ionic species to impart dispersibility. Additionally, HIPR process allows the preparation of highly stabilized dispersions at high loadings of prepolymer 15 formulations that are relatively hydrophobic and non-ionic, and are difficult to disperse in conventional batch processes. Methods of preparing HIPR emulsions are known in the art. See, for example, U.S. Patent No. 6,087,440 as well as U.S. Patent No. 5,539,021. The dispersed phase of such emulsions exhibits close compact arrangement of spheres of generally equal radius and is 20 characterized by a volume fraction as high as 0.99. The HIPR emulsion may be stabilized by the adsorption of surfactant from the continuous phase on the surface of the dispersed particulates. For the purposes of this invention, the term "continuous phase liquid stream" is used to denote a flowing liquid in which colloidal polymer particles are dispersed. Similarly, the 25 term "dispersed phase liquid stream" is used to denote a flowing liquid that becomes the dispersed phase. Additionally, the tern "dilution phase liquid stream" is used to denote a flowing liquid in which colloidal polymer particles are further dispersed. For the purposes of this specification, the term "liquid" is used to mean a homogeneous solution that can be pumped through a conduit. The liquid may be neat (that is, a liquid at room temperature) as 30 well as molten (that is, a liquid at a temperature above room temperature). The aqueous non-ionic hydrophilic polyurethane dispersions of the instant invention are prepared by continuously merging a continuous phase liquid stream having a flow rate R, and a disperse phase liquid stream having a flow rate R 2 ; and mixing the merged streams at a mixing rate sufficient to form the HIPR emulsion. The continuous phase and disperse phase 9 WO 2007/136991 PCT/US2007/068466 liquid streams are sufficiently immiscible with each other to be emulsifiable. Polydispersity ("PDI") of emulsions defines the number of species per unit of the mixture. This continuous process facilitates the control of the PDI of the dispersions. This is an important tool to control solids content of the dispersions. For the purposes of this invention, the term 5 "polydispersity" is the ratio of volume and number averages and is defined as: PDI [d En de Enuld Yn wherein number average particle size distribution Enid "En i 10 volume average particle size distribution d, =

'

weight average particle size distribution " En Id i surface average particle size distribution 15 d = n d T_ En id i where d,, is the number average particle size, ni is the number of particles of diameter di. Low PDI is an indication of narrow particle size distribution, and ability to control particle formation in a dispersion by a polymerization process. It is further a function of the particle size of the polyurethane prepolymer dispersed in the water phase. Thus, the total 20 solid content of the polyurethane dispersions of the invention can be controlled by the particle size and polydispersity index (PDI) of the polyurethane particles. A PDI of 1.0 is an indication of monodispersed polymeric particles. The polydispersity of the polyurethane particles in the invention typically ranges from 1. 1 to 10.0, preferably 1.5 to 6, and more preferably 1.1 to 2.0. 25 The aqueous non-ionic hydrophilic polyurethane dispersions of the instant invention are formed by continuously merging, in the optional presence of an emulsifying and 10 WO 2007/136991 PCT/US2007/068466 stabilizing effective amount of surfactant and/or chain extender agents, a continuous phase liquid stream containing water flowing at a rate R 1 , together with a disperse phase liquid stream containing the polyurethane prepolymer flowing at a rate R 2 under reaction conditions sufficient to form a polyurethane dispersion wherein the ratio of R 2 :R may be in the range of 5 10:90 to 30:70. All individual values and subranges from 10:90 to 30:70 are included herein and disclosed herein; for example, 20:80. The aqueous non-ionic hydrophilic polyurethane dispersions may further be diluted. For example, the aqueous non-ionic hydrophilic polyurethane dispersions may be merged and mixed with a dilution phase liquid stream containing water and optionally chain extender agents. 10 Although it is possible to first dissolve the prepolymer in a solvent prior to forming the high internal phase ratio (HIPR) emulsion, it is preferred to prepare the aqueous non-ionic hydrophilic polyurethane dispersion of the instant invention in the substantial absence of a solvent, more preferably in the absence of a solvent. The inclusion of a solvent often adds an unnecessary expense to the manufacture of the end-use product as well as health and 15 environmental concerns. In particular, solvent removal, when necessary to obtain acceptable physical properties of the product, is also an expensive as well as a time-consuming step. The resulting aqueous non-ionic hydrophilic polyurethane dispersions have a particle size sufficient to make them stable. The aqueous non-ionic hydrophilic polyurethane dispersions of the present invention will have a particle size of from 20 to 1,000 nm. All 20 individual values and subranges from 20 to 1,000 nm are included herein and disclosed herein; for example, from 40 to 1000 nm; or in the alternative, from 40 to 200 nm. Once the aqueous non-ionic hydrophilic polyurethane dispersions reach their destination for end use, they may further be diluted with sufficient amounts of water to facilitate the control of the final solid content of the dispersion, 25 The aqueous non-ionic hydrophilic polyurethane dispersions of the present invention exhibit high shear stability sufficient to be pumped in pipes in production facilities and application fields, to be shipped over long distances at various temperatures and humidity, and to be formulated with other additives. The dispersions even at high solids and high viscosities remain stable and can be diluted to lower solids content and lower viscosities. 30 The aqueous non-ionic hydrophilic polyurethane dispersions of the present invention can be used in many different applications. For example, the aqueous non-ionic hydrophilic polyurethane dispersions of the present invention can be incorporated into non-woven materials, woven textiles, gauze, paper, films, foams, or their precursors, through coating, spraying, molding, extrusion, saturation, frothing or similar techniques to regulate moisture 11 WO 2007/136991 PCT/US2007/068466 and vapor transmission, enhance fluid absorption and retention capacity, function as a barrier to gases and fluids, or move moisture away from the composite material's contact surface. The dispersion can also function to incorporate, encapsulate, bind and/or deliver various chemicals and compounds used to enhance the properties of the composite material in 5 household and institutional cleaning, apparel, personal care, healthcare, dental care, laundry, filtration, fragrance delivery, footwear, and agricultural applications. The aqueous non-ionic hydrophilic polyurethane dispersions of the present invention can also be utilized to produce a free film through casting, spraying, molding, injection, frothing or similar techniques with or without a variety of active chemicals or compounds 10 that can be utilized in these same applications. Furthermore, these dispersions could be blended with other latexes and polymers. Further examples of end-use applications of the aqueous non-ionic hydrophilic polyurethane dispersions of the present invention include, but are not limited to, the following: 1) Wound dressings and first aid dressings with enhanced absorbency and/or 15 incorporating various antiseptic, antimicrobial, antiviral, or antifungal and compounds or as an adhesive for adhering dressing to the skin; 2) Disposable or reusable washcloths containing soaps, surfactants, antimicrobial, antiviral, or other antiseptic compounds used to clean and/or sanitize human or animal skin; 20 3) Disposable or reusable wipes, towels, or foams containing active compounds used in personal care applications to cleanse, rehydrate or moisturize skin, reduce skin wrinkles, treat acne, eczema, rashes, insect bites or stings, or other skin disorders; 4) Disposable or reusable wipes, towels, or foams containing active compounds used to deliver sunscreen, sun block, fragrance, or insect repellant chemicals and 25 compounds. 5) Disposable or reusable wipes, towels, foams, or sponge material containing chemicals and compounds used for household or institutional hard surface cleaning and sanitizing such as countertops, sinks, appliances, cutting surfaces, utensils, dishes, glassware, bathroom surfaces, furniture, or windows; 30 6) Disposable or reusable sheets containing chemicals and compounds used as softeners and static reducing agents in clothing or used to launder clothing; 7) Disposable or reusable toweling materials used in household, commercial, or institutional applications to control spills and absorb fluids; 12 WO 2007/136991 PCT/US2007/068466 8) Baby diapers, child training pants or adult diapers to optimize fluid absorption, fluid retention, or moisture management and/or to deliver chemicals and compounds to reduce skin chaffing, irritation, infection risk, or to reduce or mask malodor; 5 9) Disposable or reusable toweling material containing static dissipative chemicals and compounds for cleaning of electronic equipment, electronic equipment, computer screens and keyboards, or clean room and laboratory surface areas; 10) Disposable bed linen and underpads used on institutional, commercial, or household beds; 10 11) Disposable or reusable cosmetic applicator or cosmetic removal pads and devices; 12) Disposable or reusable lens cleaning tissues for eyewear; 13) Disposable or reusable apparel used by healthcare, dental care, EMS, hazardous material handling or abatement personnel; 14) Disposable or reusable healthcare drapes and packs; 15 15) Disposable surgical drapes; 16) Disposable or reusable footwear insoles, midsoles, or accessory products designed to be inserted in footwear to optimize comfort, control perspiration, and/or minimize malodor; 17) Disposable or reusable air or fluid filtration media; 20 18) Topically sprayed free films used in agricultural applications to function as a barrier to weed germination or growth; control erosion; deliver agricultural nutrients, pesticides, herbicides, growth stimulants, or mold inhibiting chemicals and compounds; deliver and entrap seed; and/or to absorb and retain water to enhance plant root development and growth; 25 19) Sub-surface injected material around tree and plant roots to enhance water retention, act as a thermal barrier, and/or deliver chemicals and compounds necessary to restore plant health, and/or enhance plant vigor; 20) Sub-surface injected material into soil to enhance water absorption and retention and/or deliver chemicals and compounds necessary to rejuvenate the soil, or 30 optimize earthworm health and reproduction; and 21) Substrate laminating or skin contact adhesive, or adhesive component, used in medical, apparel, textile, industrial, construction, household and personal care applications. 13 WO 2007/136991 PCT/US2007/068466 From the foregoing, it will be observed that numerous variations and modifications may be effected without departing from the true spirit and scope of the novel concepts of the invention. The following non-limiting examples, and comparative demonstrations, bring out the more salient features of this invention. 5 Test Methods Test methods include the following: Particle size and particle distribution was measured via Dynamic Light Scattering (Coulter LS 230). 10 Viscosities of the prepolymers were measured according using AR 2000 Rheometer (TA Instrument). Isocyanate content (Percent NCO) was determined using a Meter Toledo DL58. Examples 15 The following examples illustrate the present invention but are not intended to limit the scope of the invention. Aqueous non-ionic hydrophilic polyurethane dispersions, as shown in Examples 1-3 of Table I, were prepared according to instant invention. Non-woven substrates impregnated with the aqueous non-ionic hydrophilic 20 polyurethane dispersions, as shown in Examples A-D of Table II, were prepared according to instant invention. Furthermore, a non-woven substrate impregnated with a control polyurethane dispersion, as shown in the comparative Example E, was also prepared under the same conditions as Examples A-D. Examples A-D and the comparative Example E were tested for their water absorption 25 capabilities under the same conditions, and the results are shown in Table III. The dried impregnated samples were weighted and then submerged in distilled water at 25 'C for 30 seconds. Once removed from water, excess water was removed from the surface by hand and the samples were reweighed, and the results are shown in Table III. 14 WO 2007/136991 PCT/US2007/068466 TABLE I Content Example 1 Example 2 Example 3 Pluronics IOR5 22.4 36.9 [ 21.9 Pluronics V- 52.2 36.9 51.1 4701 MDI, I-125M 23.9 24.7 25.6 Tegomer D3403 1.5 1.5 1.5 Percent NCO 5.39 5.34 5.35 Results Clear Clearear Viscosity @ 25 8871 9260 9548 0C Viscosity @ 40 3323 3406 3446 0C Particle Size ~60 <40 <40 (Dv, nm) 15 WO 2007/136991 PCT/US2007/068466 TABLE II Example No. Polyurethane Initial Weight Final Weight of Polymer Pick Dispersion No. of Substrate (g) Substrate (g) Up (g/m 2 ) (Table 1) A 3 1.55 2.56 18.8 B 3 1.66 2.09 [ 7.5 C 2 1.51 2.3 15.1 D 2 1.48 1.84 7.0 E Control --- 0 16 WO 2007/136991 PCT/US2007/068466 TABLE III Example Dry Weight Wet Weight Sample Area Water Water No. (g) (g) (M 2 ) Absorption Absorption (wt percent) (g/m2) A 0.867 2.613 0.018 201 96 B 0.729 1.595 0.020 119 43 C 0.766 2.301 0,017 200 88 D 0.583 1.43 .016145 52 E 0.501 0.66 .0732 9 17

Claims

1. A coraiuious process for producing a non ionic hydrophi ic aqueous polyurethane dispersion, Wherein the aqucous ionionic hydrophilic po.yurethane dispersion has 'a particic size from 20 to 1000 nm and a polydispersity in the range of 1 0 to 5.0, 5 comprising the steps or providing ai disperse phase liquid stream having a flow rate R) said disperse phase liquid stream containing a non-ionic hydrophibe polyurethane prepolymer consistingof the reaction product of: a ir. si. component, said .ir!t component being an aromatic 0 polyisocyanate, aliphatic polyisocyanate or combinations thereof; 8aid awonatic polyisocyanate being, seleted from the gmup. omsisting of MDI, TDL, -and PMDf, and said aliphatic.polyisocyanate being se1ceted frori. the grmup consisting oqfHDI. IPDI -and H 12 MDT 5 the non-ionic hydrophilic. polyurethane propolymer cor-npriing up to 90 percent by weight of the first cornponenlt, based on the weight of the non-ionic h-ydrophiico polyur-ethane prepolymer, a.id a second component, said second component being 'a non-ionic hydrophilic alkylene' oxde polyol, a non .ionic hydrophilic alkylene oxide rnonol, or G combinations thereof; said hydrophilic alkylene oxide polyol or said hydrophilic alkylone oxide monal being a horniopolymcr' or a copolymer; the non-ionic hydrophilic' polyurethane prepoaymer comprising up to 90 percent by weight of'the second component, based on the wQight of the non-ionic hydrophilic 25 polyurethanc prepolymer providing a continuous pbas liquid stream having a ilow rate R), said continuous p1ase JEqu'id alream comprising water and optionally ani external swrfaetant;. continuouxsJy merging .said disperse phase liquid stream and said continuous 30 pihase liquid straaii into a high-shear 'dispersur, wherein R, . being in the range of 10 90 to 30:70; emulsifying said non-i.onic hydrophi lic po.lyurthaie propolyne in said water via a highshear disperser; and 1 I v ereby produjcintg said nionD-ionic hydrophilic. aqueous polyarethane disperiio)n.

2. Thd cintirfuous pticxess tor producing an a.qtwow pol)'un.flrtale di~persiotl according to Chuim s,~aid process Rfutihor -xtpti ,ing the steps of providing a diludion phase liquid streaim.:said dilution phase Ii uid strceaan & wamprising water and optioxially a chAin ex tender iigent; and i dyiing s;aid dilution phase liqI.kld :.rOAf.~ with said non-ionie Ihydrophilic iteos poyureh~n~dispersion;, thereby diluting said iiourionic hydrophilic aqueouws polymIrotham:e dispersion,

3.. T~he confiuuu process for producin. an aqueous polyurethane dispersion 0 according to eiini I or clifn 2, h ~ i .sc id ciyinc being a block copolyiner or a randoml Cup)A l'l Ornc'

4. 1:11C contivnnoimu process for pivdi ci ng anl aqueous polyur.Ctlbare dispersionj ancording to ally oriq of cJfims'I to 3, whereint said hydrophli tc alkylene oxide polyol being. polycihylcne oxide.

5 ~ ~ 5 The c-ontimu.s process for producing an auos oyrtaedseso according to any one of cl a.is I to 4, wherein said it, :R v'ait bing at.east:.20: .

6; The continuous process for producing an qom olrchediprir accOrding to any one oF claim Ito1 4, Whereift stidR 2 :Rl ratio'boing at least 10.'90.

7. A polyurtlt 1iari polymer co-ated iubstrate prepared by a process c(rnprisingth 20 ste-Ps of;, pre.piva~r o-oi hydrophilc. aiqueo-us po01y u retnanc .dil'O.per,,ioi according to any-oncof caimr.s 1 to.6; applying s_aid non-ionic hydrophi-lic aqueous pollvurcfthane disporsion. to a glib;, rate"; 25 dehydrig sald inon.-ionic hydro hilic aqueoui s polyurethane dispersioni; and thereby finriiin aid fpob'uicilhan c~itod s~bslrate.

8. A polyurethane. povmcr Vipregnated sub_4,ratio. prepared b)y a process conmprising the s'tePS of: 1.9 preparg a itop-ionlO hbydrophiic~ aqueous polyurethmn. di~persion ae-Ording tW ahy odie of; claiffi 1 ,'L 6,. irinprepiauig idsbtt wt adnnoicydphi:aqv polyurethale, dispersion; 5 dehydrating said noni-ionic hydrophilic tqueous polyuiethanv. dispzrsion; mnd thereby forming said ~i1'~tai xpentdsubstrate..

9. An aqueous non- ionic hydrophilic polyarothano dispersion ohlained by the continuou011,S process according to any one of &Iairns I to 6.